Liquid vinylidene-terminated polymers

ABSTRACT

Liquid vinylidene (CH2=C&lt;) terminated polymers are prepared by the reaction of a (1) liquid polymer having a terminal functional group selected from the group consisting of carboxyl, hydroxyl, mercaptan, amine and epoxy and (2) a compound containing both an epoxy group (CH2-CH-)  ANGLE  O  and a vinylidene group. The reaction can be catalyzed using a base. The polymers cure readily to solid elastomers which are useful as sealants, caulks, potting compounds, coatings and the like.

United States Patent 1 [111 3,910,992

Skillicorn Oct. 7, 1975 LIQUID VINYLlDENE-TERMINATED POLYMERS PrimaryExaminer-Robert Gerstl Assistant ExaminerPaul J. Killos [75] Inventor.gpltilglas E. skllhcorn, Avon Lake, Attorney, Agent or Firm Alan A.Csomos [73] Assignee: The B. F. Goodrich Company [57] ABSTRACT Ak h' lron 10 Liquid vinylidene (CH =C terminated polymers are Filedi p 1972prepared by the reaction of a (1) liquid polymer hav- App]. No.: 292,926

[52] US. Cl. 260/485 G; 260/79.5; 260/82.3; 260/83.5; 260/85.5 ES;260/89.5; 260/88.3 A; 260/484 P; 260/486 B; 260/589 R; 260/609 R;260/615 R [51] Int. Cl. C07C 69/34 [58] Field of Search 260/484 R, 484P, 484 B, 260/485 G [56] References Cited UNITED STATES PATENTS3,432,478 5/1969 May 260/485 3,485,732 12/1969 DAlelio 260/485 ing aterminal functional group selected from the group consisting ofcarboxyl, hydroxyl, mercaptan, amine and epoxy and (2) a compoundcontaining both an epoxy group (ca caand a vinylidene group. Thereaction can be catalyzed using a base. The polymers cure readily tosolid elastomers which are useful as sealants, caulks, pottingcompounds, coatings and the like.

3 Claims, N0 Drawings LIQUID VINYLIDENE-TERMINATED POLYNEERS BACKGROUNDOF THE INVENTION Liquid polymers containing vinylidene (CH =C groups areknown. These polymers are prepared in a number of processes such ascleavage or degradation of high molecular weight dienic elastomers (US.Pat. No; 3,313,793 and 'British Pat. Noxl 057,014); the freeradicalpolymerization of dienic monomers in the presence of large amounts ofchain transfer agent; the solution polymerization of dienic monomersusing lithium catalysts; and addition methods such as the polyadditionof dithiols with alene' (Journal of Polymer Chemistry, Part C,Vol. 24,Page 113 (1968)).

These liquid polymers are cured through the vinylidene groups to solidelastomers. This has advantages in that compounding ingredients maybesimply dissolved or dispersed in the polymer bymixing, and'thecompounded liquid poured or spread into place. Desirably', thecompounded liquid will then quickly cure in situ at room temperature orwith only slight application of heat. Unfortunately, the vinylidenegroups of the previouslyv known polymers are not highly reactive at roomtemperature. Cure to a dry elastomeric state may often take weeks. Thishas heretofore hindered or prevented the use of these liquid polymers inapplications such as commercial caulks and sealants. Furthermore, mostof these liquid polymers have their vinylidene groups pendant to thepolymer backbone. This is not favorable for, in the vulcanized state, anoptimum balance of tensile strength and extensibility is achieved whenthe cure sites are located at the terminal ends of the liquid polymermolecule. This disadvantage cannot be readily remedied as mostpreparation processes allow for little control over the location of thevinylidene group on the molecule. Liquidpolymers containing terminalvinylidene groups are desirable, particularly if the vinylidene groupsare of high activity that readily react with curing agents at roomtemperature to form solid elastomer'.

SUMMARY OF THE INVENTION Liquid vinylidene (CH =C terminated polymers ofthe structure OH OH wherein B is a polymeric backbone of carbon-carbon,polyether, or polysulfide linkages; Z is selected from the groupconsisting of -O, S, --NH,

and OCH CH A is a bivalent radical containing 1 to atoms of C, O. S orN; and R is hydrogen or an alkyl radical containing l to4 carbon atoms,cure readily at room temperature to a dry surface. The polymers areprepared by the reaction of 1 a liquid polymer having a terminalfunctional group selected from the group consisting of carboxyl,hydroxyl, mercaptan, amine and epoxy, and (2) a compound containing bothan epoxy group and'a vinylidene group. The reaction can be catalyzedusing a base.

DETAILED DESCRIPTION The novel liquid polymers are characterized byhaving reactive terminal vinylidene (CH =C groups. The polymers have atheoretical reactive vinylidene functionality of 2.0; i.e., one reactivevinylidene group at each endof the polymer molecule. However, the novelvinylidene-terminated polymers can be prepared from liquid polymerswhich have an average functionality of less than 2: Because of this; andalso due to incomplete conversions, the novel polymers can have anaverage reactive vinylidene functionality as low as about 1.2. Theliquid polymer reactants used 'to prepare the novelpolymers can alsohave additional carboxyl, hydroxyl, mercaptan, amine, or epoxyfunctional groups as pendant groups. When such a polymer reactant isemployed, the novel polymers can have more than 2, and up to about 12reactive vinylidene groups. Therefore, the novel polymers can have anaverage re- 'active vinylidene functionality of from about 1.2 to about12. More preferredly, the novel polymers have an average reactivevinylidene functionality of from about 1.6 to about 4.

The liquid vinylidene-terminated polymers have a molecular weight offrom about 1,000 to about 20,000

as measured. using a Mechrolab Vapor Pressure Osmometer. The polymersare more conveniently described by their bulk viscosity. The polymershave a bulkviscosity of from'about 500 centipoises to about 8,000,000centipoises (measured at 27C. using a Brookfield model LVT viscometerwith spindle N0. 7 at 0.5 to rpm). More preferredly, the polymers have abulk viscosity from about 5,000 centipoises to about 2,000,000centipoises. Polymers having a bulk viscosity from about 10,000centipoises to about 400,000centipoises are particularly useful incaulk, sealant, and potting compound applications.

The novel polymers are preparedby the reaction of 1 a liquid polymerhaving from about 1.5 to about.l2 functional groups per molecule capableof reacting with an epoxy group, and (2) a compound containing both anepoxy group and a vinylidene group. Liquid polymer reactants havingterminal functional groups capable of reacting with an epoxy groupinclude (A) liquid carboxyl-terminated polymers, (B) 7 liquidmercaptanterminated polymers, (C) liquid hydroxyl-terminated polymers,.(D) liquid aminetenninated polymers,and (E) liquid epoxy-terminatedpolymers. These polymers have molecular weights and bulk viscosities inthe same range as described hereinfor the vinylidene-terminatedpolymers. The functional group, which can be carboxyl. hydroxyl,mercaptan, amine, or epoxy, comprises .from about 0.5 percent to about10 percent by weight based upon the. weight of the polymer. Morepreferredly, the functional group comprises about I percent to about 5percent by weight of the polymer.

The functionally terminated polymers have polymeric backbones comprisingcarbon-carbon linkages, polyether linkages, or polysulfide linkages. Thepolymers having carbon-carbon linkages contain polymerized units of avinylidene monomer selected from (a) monoolefins containing 2 to about 8carbon atoms such as ethylene, propylene, isobutylene, l-butene,lpentene, l-hexene, and the like; (b) dienes containing 4 ,to about 10carbon atoms such as butadiene, isoprene, 2-isopropyl-1,3-butadiene,chloroprene, and the like; (c)-vinyl aromatics such as styrene, a-methylstyrene, vinyl toluene, and the like; (d) vinyl nitriles such asacrylonitrile, methacrylonitrile, and the like; (e) vinyl and allylesters such as vinyl acetate, vinyl propionate, allyl acetate, and thelike; (f) vinyl and allyl ethers such as vinyl methyl ether, allylmethyl ether, and the like; (g) divinyls and diacrylates such as divinylbenzene, divinyl ether, dicthylene glycol diacrylate, and

the like; and (h) acrylates of the formula wherein R is H, CH or C H andR" is an alkyl radical containing 1 to 1 8 carbon atoms or analkoxyalkyl, an alkylthioalkyl, or cyanoalkyl radical containing 2 toabout 12 carbon atoms. Examples of such acrylates are ethyl acrylate,butyl acrylate, hexyl acrylate, 2- ethylhexyl acrylate, dodecylacrylate, octadecyl acrylate, methoxyethyl acrylate, butoxyethylacrylate, hexyl thiocthyl acrylate, ,B-cyanoethyl acrylate, cyanooctylacrylate, methyl methacrylate, octyl methacrylate, ethyl ethacrylate,and the like. Often two or more types of polymerized monomeric units arecontained in the polymeric backbone.

Examples ofliquid carboxyl-terminated polymers are carboxyl-terminatedpolyethylene, carboxylterminated polybutadiene, carboxyl-terminatedpolyisoprene, carboxyl-terminated poly( butadieneacrylonitrilecarboxyl-terminated poly( butadienestyrene), carboxyl-terminated poly(butadieneacrylonitrile-acrylic acid), carboxyl-terminated poly- (ethylacrylate), carboxyl-terminated poly(ethyl acrylate-n-butyl acrylate),carboxyl-terminated poly(nbutyl acrylate-acrylonitrilecarboxyl-terminated poly(butyl acrylate-styrene), and the like. Thepolymers can be prepared by free radical polymerization usingcarboxyl-containing initiators and/or modifiers as disclosedin U.S. Pat.No. 3,285,949 and German Pat. No. 1,150,205, and polymers prepared bysolution polymerization using lithium metal or organometallic compoundsand post-treating the polymers to form carboxyl groups as disclosed inU.S. Pat. Nos. 3,135,716 and 3,431,235. Liquid carboxyl-terminatedpolymers as carboxyl-terminated polybutadiene, carboxylterminatedpolybutadiene-acrylonitrile, and carboxylterminated polyacrylate werefound to be excellent reactants for the preparation of the novelpolymers.

Examples of liquid mercaptan-terminatcd polymers aremercaptan-terminated polybutadiene, mercaptanterminated polyisoprene,mercaptan-terminatcd poly(- butadiene-acrylonitrile),mercaptan-terminated poly- (ethyl acrylate), mercaptan-terminatedpoly(ethyl acrylate-n-butyl acrylate), mercaptan-terminated poly- (ethylacrylate-n-butyl acrylate-glycidyl acrylate), and the like. The polymerscan be prepared by free-radical polymerization of monomers in thepresence of dixanthogen disulfide and then post-reacted to form themercaptan groups as disclosed in U.S. Pat. Nos. 3,449,301 and 3,580,830and British Pat. No. 859,470. They can also be mercaptan-terminatedpolyethers as disclosed in Journal of Polymer Science, Vol. 12 (1968),Page 107; and mercaptan-terminated polyalkylene sulfides.

Examples of liquid hydroxyl-terminated polymers are hydroxyl-terminatedpolyethylene, hydroxylterminated polybutadiene, hydroxyl-terminatedpolyisoprene, hydroxyl-terminated poly(butadieneacrylonitrile),hydroxyl-terminated poly(acrylates), and the like. The polymers can beprepared by postreacting carboxyl-terminated polymers as disclosed inU.S. Pat. Nos. 3,551,471 and 3,551,472; by freeradical polymerization ofmonomers using hydroxylcontaining initiators as in U.S. Pat. No.2,844,632; and by solution polymerization using lithium ororganometallic catalysts and post-reacting the product to form thehydroxyl groups as disclosed in U.S. Pat. Nos. 3,135,716 and 3,431,235.

Examples of liquid amine-terminated polymers are the amine-terminatedpoly(2-methyl ethoxy) polymers and the glycol polyamines disclosed inU.S. Pat. No. 3,306,809.

Examples of liquid epoxy-terminated polymers are glycidyl ethers ofpolyhydric alcohols such as glycerol, pentaerithritol, polyvinylalcohol, 1,3,5- trihydroxybenzene, and the like; the glycidyl ethers ofpolyhydric phenols such as bisphenol A resins and of phenol-formaldehydeproducts such as the Novolac resins; and other epoxies as disclosed inU.S. Pat. No. 3,310,601.

The liquid polymer reactants can contain more than one type offunctional group. For example, the polymer can have terminal carboxylgroups and internal pendant epoxy groups derived from interpolymerizedunits of glycidyl acrylate monomer. Or, the polymer can contain terminalmercaptan groups and internal pendant carboxyl groups derived frominterpolymerized units of acrylic acid.

The novel liquid vinylidene-terminated polymers are prepared in aprocess comprising the reaction of a liquid functionally-terminatedpolymer as described above with a compound containing both an epoxy anda vinylidene group. These compounds have the formula wherein R ishydrogen or an alkyl radical containing 1 to 4 carbon atoms, and A is abivalent radical containing 1 to about 10 atoms selected from C, O, Sand N.

More preferredly, the compound contains a glycidyloxy structure as and Ris hydrogen or a methyl radical. Examples of the more preferredcompounds are isopropenyl glycidyl ether, allyl glycidyl ether,methallyl glycidyl ether, glycidyl acrylate, and glycidyl methaerylate.Most pre-, ferred are glycidyl acrylate and glycidyl methaerylate. Theliquid vinylidene-terminatedpolymers have the structure R R R R OH OHwherein B is a polymeric backbone of carbon-carbon,

polyether, or polysulfide linkages; Z is selected from the groupconsisting of O, S-, NH,

or the epoxy group of the epoxy-terminated polymer yielding the OCH CHThe radical A originates from the compound containing both the epoxy andthe vinylidene group. More preferredly, A is which is derived from theuse of glycidyl acrylate or glycidyl methaerylate, CH OCH which isderived from the use of allyl glycidyl ether or methallyl glycidylether, or CH O whichis derived from the use of isopropenyl glycidylether. The polymeric backbone B originates from the polymeric backboneof the functionally-terminated polmyer reactant.

The liquid carboxyl-terminated polymers were found to be excellentpolymer reactants for the reaction. The liquid carboxyl-terminatedpolymers have an average functionality of from about 1.5 to about 12,and more preferredly from about 1.8 to about 4. The averagefunctionality can be determined by multiplying the molecular weight ofthe polymer by the equivalent parts per hundred of carboxyl groups. Themolecular weight can be measured using a Mechrolab Vapor PressureOsmometer. The equivalent parts per hundred of carboxyl groups isdetermined by measuring the weight percent of carboxyl groups in thepolymer (by titration of a polymer solution to a phenolphthaleinend-point using alcoholic KOH) and dividing the resultant figure by45,.the weight of a carboxyl group (COOH).

The liquid carboxyl-terminated polymers employed have a molecular weightranging from about 1,000 to about 20,000 and a bulk viscosity from about1,000 to about 8,000,000 centipoises, preferably from about 5,000 to2,000,000 centipoises, measured at 27C. using a Brookfield LVTViscometer with spindle No. 7 at 0.5 to rpm.

The carboxyl-terminated polymers are reacted with a compound containingboth an epoxy and a vinylidene group, at a range of from about 1 mole toabout 3 moles of epoxy to every 1 mole of carboxyl. Use of over 3 molesof epoxy per mole of carboxyl is not necessar to achieve excellentresults.

The reaction can be conducted in bulk, preferably employing an excess ofthe epoxy-vinylidene com-.

pound. More preferredly the reaction is conducted in a solvent. Thechoice ofsolvent is influenced by the solubility of the liquidfunctionally-terminated polymer used. Examples of useful solvents arealiphatic hydrocarbons such as heptane, hexane, acetone, methylethylketone, isopropyl alcohol, t-butyl alcohol, and the like. Acetone wasfound to be an excellent solvent for a variety of liquid polymers. 0

The reaction temperature is from about 0C. to about 200C. A morepreferred temperature range is from about 50C. to about C. Totalreaction time varies as to the reaction temperature and to the use of acatalyst. A normal reaction time is from about 4 hours to about 24hours.The reaction is preferredly conducted in the absence of air or, oxygen.

The reaction rate between the carboxyl group and the epoxy group can beaccelerated by using a base a catalyst. The base can be an inorganicbase such as sodium hydroxide, potassium hydroxide, and metalalcoholates such as sodium ethoxide, potassium butoxide, and the like.More preferredly, the base is a tertiary amine. The tertiary amine canbe aliphatic, cyclic methyleneamines, or heterocyelic amines. Examplesof these are trimethylamine, triethylamine, triisopropyl amine,dimethylbutyl amine, dimethylbenzyl amine, methyldiphenyl amine,triethanol amine, N-methyl piperidine, N-methyl morpholine,triethylenediamine, pyridine, 4,4'-dipyridyl propane,2,4,6-tri(dimethylaminomethyl)phenol and the like.

The base is used in arange from about 0.05 to about 2 parts by weightbased on 100 parts by weight of the liquid functionally-terminatedpolymer reactant. More preferredly, the base is used at a level fromabout 0.1 part to 1 part by weight.

The vinylidene-terminated polymers can be isolated by direct dryingunder reduced pressure or by coagulation. If a base catalyst isemployed, typically an acid, such as hydrochloric acid, is added toneutralize the base prior to recovery. The solution can be coagulatedusing water, lower alkyl alcohol, or an alcohol/water solution. Thepolymer is then normally washed with water and dried under reducedpressure.

The liquid vinylidene-terminated polymers prepared from thecarboxyl-terminated polymers have Z equal to If glycidyl acrylate orglycidyl methaerylate is reacted with the carboxyl-terminated polymerthe radical A is Of course, the polymeric backbone B is the same as inthe carboxyl-terminated reactant.

I The liquid polymers have highly reactive terminal vinylidene groups.Therefore, preferredly, they are admixed with an antioxidant to hinderpremature airoxidation. The antioxidant is used in a range from about0.1 to about parts by weight per 100 parts by weight of polymer. Theantioxidants are typical antioxidants such as phenyl-B-naphthylamine,di-B-naphthylp-phenylenediamine, 2,6-di-t-butyl paracresol, 2,4,6-trihexyl phenol, l,3,5-tris( 3,S-di-t-butyl-4-hydroxyben- The thiol andamine curatives are used in a range from about 0.1 to about 20 parts byweight per lOO parts by weight of the vinylidene-terminated polymer, andmore preferably from about 0.2 to about 10 parts by weight lfa tertiaryamine cure catalyst is employed, the range of use is from about 0.01 toabout 3 parts by weight per 100 parts of polymer.

Many other compounding ingredients can be used with the liquid polymers.Such ingredients include fillers such clays, silicas, carbon blacks,resins, asbestos, and the like; plasticizers and extenders such asdiisobutyl oleate, diisooctyl sebacate, dibenzyl phthalate, ASTM oils,glycerin, and the like; antioxidants and stabilizers; pigments such asTiO iron oxide, chromium l5 zyl)isocyanurate, and other useful phenolicantioxioxlde the and tacklfiers Waxes fungicides and the like. dantsdisclosed in U.S. Pat. No. 3,157,517.

The curatives and compounding ingredients can be Thevinylidcne-termmated polymers are cured to admixed with the liquidvinylidene-terminated polysolld elastomers using known curatives forunsaturated mers using internal mixers such as Henschel mixers andliquid polymers. The curvatlves include unsaturated extruders or usingink mill rolls, and using standard rubber curatives such as sulfur,sulfur donors, tetramemixing techniques. thylthiuram dlsulfide,tetramethylene guanidlne, and Th e liquid polymers can be poured intoplace, spread the like. Because of the high activity of the vinylidene vI into place with a spatula or knife-edge, or forced into groups thepolymers i readily Cure at 9 place using a caulk gun or the like. Thepolymer cures tum to addry g cif d P g quickly at room temperature,yielding an elastomer Tl zh l f a y l ii l fi; t ggi having a drysurface. The liquid vinylidene-terminated 1 5; h 10 b d lT l g ik i i lpolymers are useful for preparing caulks and sealants eptme It t e l t10g for filling cracks and crevices, joints between brick, andmercaptoproplonates Such as Y' glycol bls( concrete slabs, glass, andthe like; potting Compounds thioglycolate), trimethyl propanetris(thioglycolate), for imbedding wires and electrical Components;pentaerythritol tetrakls(thloglycolate), ethylene glycol implacegaskets; and protective Coatings for metal bis(mercaptopropionate),trimethylol propane concrete and the like ms(mfircaptoproplonalexPemuerythmol The following Examples serve to more fully illustratetetrakis(mercaptopropionate), and the like, and other the inventionIngredients are given in parts by weight thiols disclosed in U.S. Pat.Nos. 3,310,60l and unless Otherwise indicated.

Preferredly, the thiol type curatives are used with ter- EXAMPLE I tiaryamines as catalysts. Examples of the tertiary Liquid CarbOXyHel-minatedpolybumdiene polymers ummes mmethyl amme, methyl amine were preparedfollowing the procedure given in U.S. dlmethylethyl amine, N y flmlme.trlphenyl Pat. No. 3,285,949. The polymers had the following amine,N-methyl piperidine, triethylene diamine, 4,4'- properties; dipyridylpropane, 2,4,6-tri(dimethylaminomethyl)- phenol and the i Bulk ViscosityWeight Percent Examples of primary and secondary dland poly- 4s po|ymcrcps," cdrhoxylcomcm amine curatives are ethylenediamine,trimethylenediamine, tetramethylenediamine, pentamethylene- S Q23diamine, hexamethylenediamine, 1,3- diaminocyclohexane,m-phenylenediamine, bis(hcxamethylcne )triamine, triethylene tetraamine,hexa The polymers were used to prepare liquid vinylidenemethylenetetraamine, tricretonylidene tetraamine, terminated polymers. Therecipes used and polymer and the like. data were as follows:

Polymer A I00 I00 100 lUU Polymer B lUU lOO 100 Acetone 64 64 64 64 64o4 Toluene lUO (ilycitlyl :lcrylate 8.1 8.] 8.] 9.0 9.0 9.0 Allylglycitlyl ether 7.3 a 'l'rimethyl amine.

milliliters m (H4 0.8 0.8 0.8 0.8

UMP-30:, parts l.(l l'elilperlltllrev )5 J5 L)5 )5 -95 95 Time, hours l2l2 l2 l2 lo 12 X Vinylitlene polymer.

hulk Viscosit) cps All 27%. 23.400 l l LXUU 24mm (14w 1,800,001) 188,000392.000 Residual weight percent ellrhoxyl content l .45 0.02 0.27 (l. 140.0 0. l4 0.29 Percent carhoxyl reacted 27 99 so 95 9o 94 87 '25) leight ill methzliiul "'llo-irittliliietli lillliillnmctlnll plieliul Thepolymer, solvent, and glycidyl acrylate or allyl glycidyl ether wereplaced in a glass reactor'vessel. About 0.5 part by weight based uponthe weight of the polymer of hydroquinone was added to hindercrossterminated polymer" from which the vinylideneterminatedpolybutadiene was prepared. The sample shows that no cure took place,even though the polymer is highly unsaturated and contains pendant vinyllinking reactions. The amine catalyst was then added structure theresult of polymerization of the 1,3 and the vessels agitated for thetimes and at the temperbutadiene. The quick, dry cure is achieved onlyatures indicated. After reaction, about 0.5 milliliters of through thereactive vinylidene groups. concentrated hydrochloric acid was added toneutral- Sample 14 was also evaluated by pouring it into a tenize theamine catalyst. The vinylidene-terminated polysile sheet mold'andletting it'set for 7 days at room temmers were isolated by direct dryingunder reduced perature. Thecured tensile sheet was removed and pressure.tested for tensile, elongation, and hardness following Sample 1 used noamine catalyst. The carboxyl re- ASTM D412 and ASTM D676 Durometer A.The acted, but the other samples demonstrate the accelerpolymer had a 110 psig tensile, a 500 percent elongaated reaction rate obtained byusing a base catalyst. tion, and a'Durometer A hardness of 18. TheExample shows the preparation of the vinylidenel5 EXAMPLE lll terminatedpolymers and shows that high conversions V Y are readily obtained. Theliquid vinylidene-terminated polymers of the in- EXAMPLE'" vention havehighly reactive vinylidene groups. In Example ll, the control sample, aliquid carboxyl- The liquid vinylidcne-terminated polybutadienepolterminated polybutadiene polymer did not cure in 10 ymers prepared inExample l were cured using the foldays even though the polymer containsvinyl configuralowing recipes: tion as the result of polymerized1,3-butadiene. Other Con 1 2 4 5 6 7 s 9 10 H 12 13 I4 trol Polymer l100 Polymer 2 100 Polymer 4 I00 100 100 100 100 100 Polymer 6 100 100100 I00 Polymer 7 I00 100 Ethylenediaminc L5 1.5 1.5 15 ll l.5 1 5Triethylene tetraamine .9 l,6-hexane diamine 2,6

Tetramethylene guanidinc 6 Mercaptate P-33' 8.2 8.2 4.5 4 5 Methyl tuads15 Sulfur 5 Zinc oxide 5 DMP-3O 1.0 2.0 Room temperature CUI'C Days 7 7l0 1 1 7 7 4 l 7 7 7 10 Hardness. Duro A 23 IX 2] 31 I5 6 8 No Percentelongation 1000 275 400 200 450 I 225 500- 350 900 550 Cure 16 hours atl05C.

Hardness, Duro A l6 2 l l Percent Elongation 200 800 400 800"l'rimcthylolpropane trist mercaptopropionate) "l'ctramethylthriuramdisulfide "Carlxixyl-terminatetl polybutadiene used in Example l. [00pans by weight The curatives were added to the liquid vinylideneliquidpolymers having pendant vinyl configuration terminated polymers and themix stirred to achieve uniwere also evaluated. The recipes are follows:

Polymer 4 I00 Polymer (1' 100 Hstyl B4000 100 Hstyl 3-2000 100 100 HycarI312" l00 I00 .l I00 Ethylenediamine L5 5.0 [5.0 4 2. 8.6 MercaptateP-33 .5 .2 31.3 l6.'0 47.0 DMP-30 .0 1.0 4.0 2.0 5.7 Room temperaturecure Days 7 7 7 7 7 1 7 7 7 7 Hardness, Duro A 6 No No No 18 No No No NoPercent elongation 350 I75 Cure Cure Cure 400 Cure Cure Cure (ure 16'hours at C.

Hardness, Duro A 16 No No No No No No No Percent elongation 200 CureCure Cure Cure Cure (ure Cure polymers from Example I '-'l.it uitlpolyhutntlieln: polymer liming a molecular weight of about I200 andabout a 90% by eight \in \-l configuration Liquid polybutadiene polymerhaving a molecular weight of about 2100 and about u I'd by weight \inylconfiguration Liquid polythutadiene-acrylonitrile) polymer having abouta 31 1' by weight acrylonitrile content and about a 20% by weight vinylconfiguration form distribution. The mixes were then poured into Samplesl, 2 and 6 were prepared using the novel molds and let stand at roomtemperature to cure Sam- 65 vinylidene-termi'nated polymers. Theremaining samples 10 to 13 also were also at elevated temperatures. Allof the cured samples had dry surfaces. The control sample was an attemptat curing the carboxylples were prepared using liquid polymers having ahigh degree of vinyl-configuration unsaturation. Only the novel polymerscured at room temperature and at elevated temperature, even though highlevels of curatives were employed with the other polymers. The Exampledemonstrates that the vinylidene groups of the liquid polymers of theinvention are much more reactive than either main polymer chainunsaturation or pendant vinyl unsaturation. I

EXAMPLE iv A liquid earboxyl-terminated poly( butadieneacrylonitrile)polymer was prepared following the procedure in US. Pat. No. 3,285,949.The acrylonitrile range of these polymers is from about l percent toabout 40 percent by weight based upon the weight of the polymer, andmore preferably is from about 10 percent to about 30 percent by weight.The butadiene content ranges from about 50 percent to about 98 percentby weight and the carboxyl content from about 0.5 percent to about 10percent by weight, allv weights based upon the total weight of thepolymer. The prepared polymer had a bulk viscosity at 27C. of 112,000, a2.52 percent by weight carboxyl content, and a 18.2 percent by weightacrylonitrile content. The polymer was used to prepare a liquidvinylidene-terminated poly(butadiene-acrylonitrile)polymer. The recipeused and data was as follows:

weight percent The vinylidene polymer was prepared following theprocedure given in Example 1. The polymer was cured using the followingrecipes. All samples had a dry surface.

Vinylidcne polymer 100 100 100 Ethylenetliamine 1.7 1.25 Triethylenetetraamine 0.4 1.0 Room temperature cure Days 1 1 1 Hardness, Duro A 127 30 Elongation, percent 400 100 125 EXAMPLE V Liquidcarboxyl-terminated polyacrylate polymers were prepared following theprocedure given in US. Pat. No. 3,465,058. The polymers made had thefollowing properties:

Polymer Bulk Viscosity Weight Percent cps at 27C. Carboxyl content A24,000 1.71 B 20,000 2.47 C 141,000 3.1 1

l l (Hi .=C-A- Polymer A Polymer B Polymer C Acetone (ilycidyl acrylateTrimethyl amine, milliliters DMP-30, milliliters 'lemperature, C.

Time, hours Vinylidene polymer, bulk viscosity, cps at 27C.

Residual carhoxyl content weight percent Percent carboxyl conversion Thepolymers were cured using the following recipes:

Sample 2 Sample 3 C ontrol Ethylenediamine Triethylene tetraarnine Roomtemperature eure days 1 Hardness. Duro A Elongation. percent'earhtixyl-tcrminuteil pulytn-butyl acrylate-cthyl acrylate-aerylicacid) cure EXAMPLE V1 A liquid vinylidene-terminated polyether polymerwas prepared from a liquid amine-terminated polyether. Theamine-terminated polyether has the formula wherein x is from about 5 to40. The polymer had a value of of about 30, a bulk viscosity at 27C. of236 cps., and a weight percent nitrogen content of 1.4 percent. Thepolymer was reacted at 100 parts by weight with 51.8 parts by weight ofglycidyl acrylate in 100 parts by weight of acetone, following theprocedure given in Example 1. The liquid vinylidene-terminated polyetherpolymer had a bulk viscosity at 27C. of 500 cps. The vinylidene polymerwas mixed at 100 parts by weight with 3.5 parts by weight ofethylenediamine. After 10 days at room temperature, the mix was a solidelastomer having a Duro A hardness of 5 and a 30 percent elongation.

The liquid vinylidene polymers prepared from the amine-terminatedpolymers have the formula wherein R is defined as above and is from toabout 40. The polymer preparedin the example has A equal 120 and x equalto 30.

I claim:

1. A liquid vinylidene-terminated polymer having a molecular weight offrom about 1,000 to about 20,000 of the structure OH OH wherein B is apolymeric backbone of carbon-carbon linkages and consisting ofpolymerized units of dienes containing 4 to about carbon atoms; A isselected from the group consisting of CH OCH and CH O; and R is hydrogenor an alkyl radical containing 1 to 4 carbon atoms.

2. A liquid vinylidene-terminated polymer of claim 1 having a molecularweight from about 1,000 to about 20,000 of the structure O R ll I

1. A LIQUID VINYLIDENE-TERMINATED POLYMER HAVING A MOLECULAR WEIGHT OFFROM ABOUT 1,000 TO ABOUT 20,000 OF THE STRUCTURE
 2. A liquidvinylidene-terminated polymer of claim 1 having a molecular weight fromabout 1,000 to about 20,000 of the structure
 3. A polymer of claim 2wherein the diene monomer is 1,3-butadiene and R is hydrogen or a methylradical.